WO2014031962A1 - Mélanges de réfrigérants comprenant des tétrafluoropropènes, du difluorométhane, et éventuellement du difluoroéthane et leurs utilisations - Google Patents

Mélanges de réfrigérants comprenant des tétrafluoropropènes, du difluorométhane, et éventuellement du difluoroéthane et leurs utilisations Download PDF

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Publication number
WO2014031962A1
WO2014031962A1 PCT/US2013/056396 US2013056396W WO2014031962A1 WO 2014031962 A1 WO2014031962 A1 WO 2014031962A1 US 2013056396 W US2013056396 W US 2013056396W WO 2014031962 A1 WO2014031962 A1 WO 2014031962A1
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Prior art keywords
refrigerant
composition
hfo
weight percent
component
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PCT/US2013/056396
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English (en)
Inventor
Barbara Haviland Minor
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E. I. Du Pont De Nemours And Company
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Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to EP13831214.5A priority Critical patent/EP2888334B1/fr
Priority to ES13831214T priority patent/ES2703937T3/es
Priority to PL13831214T priority patent/PL2888334T3/pl
Publication of WO2014031962A1 publication Critical patent/WO2014031962A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
    • C09K2205/126—Unsaturated fluorinated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/40—Replacement mixtures
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
    • F25B2400/00—General features or devices for refrigeration machines, plants or systems, combined heating and refrigeration systems or heat-pump systems, i.e. not limited to a particular subgroup of F25B
    • F25B2400/18—Refrigerant conversion

Definitions

  • compositions for use in refrigeration systems wherein the composition comprises tetrafluoropropenes, difluoromethane, and optionally difluoroethane.
  • the compositions of the present invention are useful in methods for producing cooling, methods for replacing refrigerants and refrigeration apparatus.
  • compositions comprising tetrafluoropropenes, difluoromethane, and optionally difluoroethane have been found to possess suitable properties to allow their use as replacements of higher GWP refrigerants currently in use, in particular R404A, R407A, R407F and R507A.
  • compositions consist of: (A) a refrigerant component consisting essentially of (1 ) at least one refrigerant having an OEL less than 400; and (2) a combination of refrigerants, each having an OEL greater than 400, consisting essentially of (i) at least one refrigerant selected from the group consisting of HFC-32 and HFC-152a; and (ii) trans-HFO-1234ze; and optionally (B) a non-refrigerant component; wherein component (A)(2) of the refrigerant component is present in an amount sufficient to provide an overall OEL for the refrigerant component of at least 400.
  • the refrigerant mixtures of the refrigerant component are useful as components in compositions also containing non-refrigerant components (e.g. lubricants), in processes to produce refrigeration, in methods for replacing refrigerant R404A, R407A, R407F or R-507A, and in
  • FIG.1 is a plot of one embodiment of the range of compositions as claimed and specific other known data points. Each apex of the triangle corresponds to 100% of the labeled components, HFO-1234yf, HFC-32 and trans-HFO-1234ze.
  • FIG. 2 is a plot of burning velocity versus the ratio of wt% HFO-1234 to wt% HFC-152a. This plot is used to estimate burning velocities for compositions containing HFO-1234yf, HFC-32, HFC-152a and trans-HFO- 1234yf. DETAILED DESCRIPTION
  • heat transfer fluid means a composition used to carry heat from a heat source to a heat sink.
  • a heat source is defined as any space, location, object or body from which it is desirable to add, transfer, move or remove heat.
  • heat sources are spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air conditioning, industrial water chillers or the passenger compartment of an automobile requiring air conditioning.
  • the heat transfer composition may remain in a constant state throughout the transfer process (i.e., not evaporate or condense).
  • evaporative cooling processes may utilize heat transfer compositions as well.
  • a heat sink is defined as any space, location, object or body capable of absorbing heat.
  • a vapor compression refrigeration system is one example of such a heat sink.
  • a refrigerant is defined as a heat transfer fluid that undergoes a phase change from liquid to gas and back again during the cycle used to transfer of heat.
  • a heat transfer system is the system (or apparatus) used to produce a heating or cooling effect in a particular space.
  • a heat transfer system may be a mobile system or a stationary system.
  • heat transfer systems are any type of refrigeration systems and air conditioning systems including, but are not limited to, air conditioners, freezers, refrigerators, heat pumps, water chillers, flooded evaporator chillers, direct expansion chillers, walk-in coolers, mobile refrigerators, mobile air conditioning units, dehumidifiers, and
  • mobile heat transfer system refers to any refrigeration, air conditioner or heating apparatus incorporated into a transportation unit for the road, rail, sea or air.
  • mobile refrigeration or air conditioner units include those apparatus that are independent of any moving carrier and are known as “intermodal" systems.
  • intermodal systems include “container' (combined sea/land transport) as well as “swap bodies” (combined road/rail transport).
  • stationary heat transfer systems are systems that are fixed in place during operation.
  • a stationary heat transfer system may be associated within or attached to buildings of any variety or may be standalone devices located out of doors, such as a soft drink vending machine.
  • stationary applications may be stationary air conditioning and heat pumps, including but not limited to chillers, high temperature heat pumps, residential, commercial or industrial air conditioning systems (including residential heat pumps), and including window, ductless, ducted, packaged terminal, and those exterior but connected to the building such as rooftop systems.
  • the disclosed compositions may be useful in equipment including commercial, industrial or residential refrigerators and freezers, ice machines, self-contained coolers and freezers, flooded evaporator chillers, direct expansion chillers, walk-in and reach-in coolers and freezers, and combination systems.
  • the disclosed compositions may be used in supermarket refrigeration systems.
  • stationary applications may utilize a secondary loop system that uses a primary refrigerant to produce cooling in one location that is transferred to a remote location via a secondary heat transfer fluid.
  • Refrigeration capacity (also referred to as cooling capacity) is a term which defines the change in enthalpy of a refrigerant in an evaporator per pound of refrigerant circulated, or the heat removed by the refrigerant in the evaporator per unit volume of refrigerant vapor exiting the evaporator (volumetric capacity).
  • the refrigeration capacity is a measure of the ability of a refrigerant or heat transfer composition to produce cooling.
  • Cooling rate refers to the heat removed by the refrigerant in the evaporator per unit time.
  • Coefficient of performance is the amount of heat removed divided by the required energy input to operate the cycle. The higher the COP, the higher is the energy efficiency. COP is directly related to the energy efficiency ratio (EER) that is the efficiency rating for refrigeration or air conditioning equipment at a specific set of internal and external temperatures.
  • EER energy efficiency ratio
  • subcooling refers to the reduction of the temperature of a liquid below that liquid's saturation point for a given pressure.
  • the saturation point is the temperature at which the vapor is completely condensed to a liquid, but subcooling continues to cool the liquid to a lower temperature liquid at the given pressure.
  • Subcooling thereby improves refrigeration capacity and energy efficiency of a system.
  • Subcool amount is the amount of cooling below the saturation temperature (in degrees).
  • Superheat is a term that defines how far above its saturation vapor temperature (the temperature at which, if the composition is cooled, the first drop of liquid is formed, also referred to as the "dew point") a vapor composition is heated.
  • temperatures of a phase-change process by a refrigerant within a component of a refrigerant system exclusive of any subcooling or superheating.
  • This term may be used to describe condensation or evaporation of a near azeotrope or non-azeotropic composition.
  • azeotropic composition a constant-boiling mixture of two or more substances that behave as a single substance.
  • One way to characterize an azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has the same composition as the liquid from which it is evaporated or distilled, i.e., the mixture
  • compositions are characterized as azeotropic because they exhibit either a maximum or minimum boiling point, as compared with that of the non- azeotropic mixture of the same compounds.
  • An azeotropic composition will not fractionate within a refrigeration or air conditioning system during operation. Additionally, an azeotropic composition will not fractionate upon leakage from a refrigeration or air conditioning system.
  • An azeotrope-like composition (also commonly referred to as a "near- azeotropic composition”) is a substantially constant boiling liquid admixture of two or more substances that behaves essentially as a single substance.
  • azeotrope-like composition One way to characterize an azeotrope-like composition is that the vapor produced by partial evaporation or distillation of the liquid has substantially the same composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes without substantial composition change.
  • Another way to characterize an azeotrope-like composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially the same.
  • a composition is azeotrope-like if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is less than about 10 percent.
  • a non-azeotropic (also referred to as zeotropic) composition is a mixture of two or more substances that behaves as a simple mixture rather than a single substance.
  • One way to characterize a non-azeotropic composition is that the vapor produced by partial evaporation or distillation of the liquid has a substantially different composition as the liquid from which it was evaporated or distilled, that is, the admixture distills/refluxes with substantial composition change.
  • Another way to characterize a non- azeotropic composition is that the bubble point vapor pressure and the dew point vapor pressure of the composition at a particular temperature are substantially different.
  • a composition is non-azeotropic if, after 50 weight percent of the composition is removed, such as by evaporation or boiling off, the difference in vapor pressure between the original composition and the composition remaining after 50 weight percent of the original composition has been removed is greater than about 10 percent.
  • lubricant means any material added to a composition or a compressor (and in contact with any heat transfer composition in use within any heat transfer system) that provides lubrication to the compressor to aid in preventing parts from seizing.
  • compatibilizers are compounds which improve solubility of the hydrofluorocarbon of the disclosed compositions in heat transfer system lubricants. In some embodiments, the compatibilizers improve oil return to the compressor. In some embodiments, the composition is used with a system lubricant to reduce oil-rich phase viscosity.
  • oil-return refers to the ability of a heat transfer composition to carry lubricant through a heat transfer system and return it to the compressor. That is, in use, it is not uncommon for some portion of the compressor lubricant to be carried away by the heat transfer composition from the compressor into the other portions of the system. In such systems, if the lubricant is not efficiently returned to the compressor, the compressor will eventually fail due to lack of lubrication.
  • ultra-violet dye is defined as a UV fluorescent or phosphorescent composition that absorbs light in the ultra-violet or “near" ultra-violet region of the electromagnetic spectrum.
  • the fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits at least some radiation with a wavelength in the range of from 10 nanometers to about 775 nanometers may be detected.
  • Flammability is a term used to mean the ability of a composition to ignite and/or propagate a flame.
  • the lower flammability limit (“LFL”) is the minimum concentration of the heat transfer composition in air that is capable of propagating a flame through a homogeneous mixture of the composition and air under test conditions specified in ASTM (American Society of Testing and Materials) E681 -04.
  • the upper flammability limit (“UFL”) is the maximum concentration of the heat transfer composition in air that is capable of propagating a flame through a homogeneous mixture of the composition and air under the same test conditions.
  • a refrigerant In order to be classified by ASHRAE (American Society of Heating, Refrigerating and Air-Conditioning Engineers) as non-flammable, a refrigerant must be nonflammable under the conditions of ASTM E681 -04 as formulated in the liquid and vapor phase as well as non-flammable in both the liquid and vapor phases that result during leakage scenarios.
  • ASTM E681 -04 American Society of Heating, Refrigerating and Air-Conditioning Engineers
  • GWP Global warming potential
  • GWP is an index for estimating relative global warming contribution due to atmospheric emission of a kilogram of a particular greenhouse gas compared to emission of a kilogram of carbon dioxide.
  • GWP can be calculated for different time horizons showing the effect of atmospheric lifetime for a given gas.
  • the GWP for the 100 year time horizon is commonly the value referenced.
  • a weighted average can be calculated based on the individual GWPs for each component.
  • ODP Ozone depletion potential
  • the ODP is the ratio of the impact on ozone of a chemical compared to the impact of a similar mass of CFC-1 1 (fluorotrichloromethane).
  • CFC-1 1 fluorotrichloromethane
  • the ODP of CFC-1 1 is defined to be 1 .0.
  • Other CFCs and HCFCs have ODPs that range from 0.01 to 1 .0.
  • HFCs have zero ODP because they do not contain chlorine.
  • Occupational exposure limit (OEL) is an upper limit on the acceptable concentration of a substance in workplace air for a particular material or class of materials.
  • the OEL for a substance indicates the acceptable exposure over an 8 hour work day, 5 days a week for a working lifetime without adverse health effects.
  • a refrigerant with an OEL of 400 ppm or greater is classified as a class A refrigerant by ASHRAE indicating a lower degree of toxicity.
  • a refrigerant with an OEL of less than 400 ppm is classified as a class B refrigerant by ASHRAE indicating a higher degree of toxicity.
  • Other industries use different terms including TLV-TWA
  • the OEL of a mixture is the reciprocal addition of the mole fraction (mf) of each individual component divided by their respective OEL.
  • mf mole fraction
  • the changes to the WCF are determined for a vapor leak at several conditions, an example of which is a cylinder 90% full by mass and leak at the bubble point temperature of the WCF + 10 degrees C or -40 degrees C, whichever is higher, per the standard.
  • Vapor leak conditions are continued until the formulation reaches atmospheric pressure, and the Worst Case Fractionated Formulation
  • WCFF WCFF
  • OEL residual liquid or vapor composition which is expected to have the lowest OEL. If the OEL is above 400 ppm for the as formulated and for the WCFF composition, then it is considered a Class A lower toxicity refrigerant composition. If the OEL is less than 400 ppm for either the as formulated or for the WCFF composition, then it is considered a Class B higher toxicity refrigerant composition.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • transitional phrase "consisting essentially of is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term 'consisting essentially of occupies a middle ground between “comprising” and 'consisting of.
  • components of the refrigerant mixtures and the refrigerant mixtures themselves can contain minor amounts (e.g., less than about 0.5 weight percent total) of impurities and/or byproducts (e.g., from the manufacture of the refrigerant components or reclamation of the refrigerant components from other systems) which do not materially affect the novel and basic characteristics of the refrigerant mixture.
  • HFC-134a may contain minor amounts of HFC-134 as a byproduct from the manufacture of HFC-134a.
  • trans-HFO-1234ze which can be a byproduct of certain processes for producing HFO-1234yf (see e.g., US2009/0278075).
  • trans-HFO-1234ze by reciting trans-HFO-1234ze as a separate component include trans-HFO-1234ze whether or not its presence materially affects the novel and basic characteristics of the refrigerant mixture (alone or together with other impurities and/or byproducts which by themselves would not materially affect the novel and basic characteristics of the refrigerant mixture).
  • HFO-1234yf 2,3,3,3-tetrafluoropropene may also be referred to as HFO-1234yf, HFC-1234yf, or R1234yf.
  • HFO-1234yf may be made by methods known in the art, such as by dehydrofluorination 1 ,1 ,1 ,2,3-pentafluoropropane (HFC-245eb) or 1 ,1 ,1 ,2,2-pentafluoropropane (HFC-245cb).
  • Difluoromethane (HFC-32 or R-32) is commercially available or may be made by methods known in the art, such as by dechlorofluorination of methylene chloride.
  • HFC-152a or R-152a is commercially available or may be made by methods known in the art, such as by
  • 1 ,3,3,3-tetrafluoropropene may be prepared by dehydrofluorination of a 1 ,1 ,1 ,2,3-pentafluoropropane (HFC-245eb, CF3CHFCH 2 F) or 1 ,1 ,1 ,3,3-pentafluoropropane (HFC-245fa,
  • HFO-1234ze may exist as one of two configurational isomers, cis- or trans- (also referred to as the E- and Z- isomers respectively).
  • Trans-HFO-1234ze is available commercially from certain fluorocarbon manufacturers (e.g., Honeywell International Inc., Morristown, NJ).
  • compositions consisting of: (A) a refrigerant component consisting essentially of (1 ) at least one refrigerant having an OEL less than 400; and (2) a combination of refrigerants, each having an OEL greater than 400, consisting essentially of (i) at least one refrigerant selected from the group consisting of HFC-32 and HFC-152a; and
  • component (ii) trans-HFO-1234ze; and optionally (B) a non-refrigerant component; wherein component (A)(2) of the refrigerant component is present in an amount sufficient to provide an overall OEL for the refrigerant component of at least 400.
  • the worst case fractionation formulation (WCFF) of the refrigerant component has an overall OEL of at least 400.
  • the burning velocity of the overall refrigerant component of the composition is less than 10 cm/sec.
  • the refrigerant component has a GWP of less than 600.
  • the refrigerant component has a GWP of less than 500.
  • the refrigerant component has a GWP of less than 300.
  • Component (A)(1 ) is selected from refrigerant compounds with OEL less than 400.
  • Such refrigerant compounds include olefinic refrigerants.
  • Olefinic refrigerants include 1 ,1 ,1 ,2,3-pentafluoropropene (HFO-1225ye) and 2,3,3,3-tetrafluoropropene (HFO-1234yf).
  • component (A)(1 ) consists essentially of HFO-1234yf.
  • the refrigerant component of the composition is suitable for use as a replacement for R404A, R407A, R407F or R507A and consists essentially of from 4 to 32 weight percent of HFO-1234yf, from 34 to 38 weight percent of HFC-32, and from about 32 to about 60 weight percent of trans-HFO-1234ze.
  • the refrigerant component of the composition consists essentially of mixtures of HFO-1234yf, HFC-32, and trans-HFO-1234ze containing from 4 to 16 weight percent, from 4 to 17 weight percent, from 4 to 18 weight percent, from 4 to 19 weight percent, or from 4 to 20 weight percent of HFO- 1234yf.
  • the refrigerant component contains from 34 to 37 weight percent, from 34 to 36 weight percent, or from 34 to 35 weight percent of HFC-32. And also in another embodiment, the refrigerant component contains from 40 to 60 weight percent, from 42 to 60 weight percent, from 44 to 60 weight percent, from 46 to 60 weight percent, or from 48 to 60 weight percent of trans-HFO-1234ze.
  • the refrigerant component of the composition consists essentially of from 4 to 16 weight percent of HFO-1234yf, from 34 to 38 weight percent of HFC-32, and from about 48 to about 60 weight percent of trans-HFO-1234ze.
  • the refrigerant component of the composition consists essentially of from 4 to 8 weight percent of HFO-1234yf, from 34 to 38 weight percent of HFC-32, and from about 56 to about 60 weight percent of trans-HFO-1234ze.
  • FIG. 1 shows that one embodiment of the range of the claimed compositions, from 4 to 16 weight percent HFO-1234yf, from 34 to 38 weight percent HFC-32, and from 48 to 60 weight percent trans-HFO- 1234ze does not incorporate compositions previously disclosed.
  • the compositions shown by the points in FIG. 1 are:
  • compositions A through G fall outside of the ranges as claimed herein. Additionally, compositions A through G have been found to fractionate in such a manner as to produce compositions with OEL less than 400 (if the HFO-1234yf is set at 100 or lower). Thus, compositions A through G would be classified as Class B refrigerants (higher toxicity) by ASHRAE (per ASHRAE Standard 34), should the OEL for HFO-1234yf be set at 100 or lower.
  • Compositions of the present invention containing HFO-1234yf, HFC-32 and trans-HFO-1234ze provide nominal compositions, as well as, WCFF compositions with OEL which exceeds 400 ppm indicating Class A lower toxicity per ASHRAE Standard 34-2010. Additionally, these compositions have burning velocities less than 10 cm/sec establishing 2L lower flammability classification according to ASHRAE Standard 34-2010.
  • the refrigerant component of the composition is suitable for use as a replacement for R404A, R407A, R407F or R507A and consists essentially of from 5 to 39 weight percent of HFO-1234yf, from 34 to 38 weight percent of HFC-32, from about 10 to 16 weight percent HFC-152a, and from about 13 to about 45 weight percent of trans- HFO-1234ze.
  • the refrigerant component of the composition consists essentially of mixtures of HFO-1234yf, HFC-32, and trans-HFO-1234ze containing from 5 to 19 weight percent, from 5 to 20 weight percent, from 5 to 21 weight percent, from 5 to 25 weight percent, from 5 to 28 weight percent, from 5 to 30 weight percent, from 5 to 33 weight percent, or from 5 to 35 weight percent of HFO-1234yf.
  • the refrigerant component contains from 34 to 37 weight percent, from 34 to 36 weight percent, or from 34 to 35 weight percent of HFC-32.
  • the refrigerant component contains from 1 1 to 16 weight percent of HFC-152a.
  • the refrigerant component contains from 18 to 45 weight percent, from 20 to 45 weight percent, from 23 to 45 weight percent, from 28 to 45 weight percent, from 30 to 45 weight percent, or from 32 to 45 weight percent of trans-HFO-1234ze.
  • the refrigerant component of the composition consists essentially of from 5 to 19 weight percent of HFO-1234yf, from 34 to 38 weight percent of HFC-32, from 1 1 to 16 weight percent of HFC- 152a, and from about 32 to about 45 weight percent of trans-HFO-1234ze.
  • the refrigerant component of the composition consists essentially of from 5 to 9 weight percent of HFO-1234yf, from 34 to 38 weight percent of HFC-32, from 12 to 16 weight percent of HFC- 152a, and from about 41 to about 45 weight percent of trans-HFO-1234ze.
  • compositions of the present invention containing HFO-1234yf, HFC- 32, HFC-152a and trans-HFO-1234ze provide nominal compositions, as well as, WCFF compositions with OEL which exceed 400 ppm indicating Class A lower toxicity per ASHRAE Standard 34. Additionally, these compositions have burning velocities less than 10 cm/sec establishing 2L lower flammability classification according to ASHRAE Standard 34.
  • component (A)(1 ) is selected from refrigerants which have an OEL of about 200 or less. Such refrigerants may include HFO-1225ye and HFO-1234yf. In another embodiment, component (A)(1 ) is selected from refrigerants which have an OEL of about 100 or less. Such refrigerants may include HFO-1225ye and HFO-1234yf.
  • HFO-1234yf and mixtures containing HFO-1234yf are being
  • R-404A (ASHRAE designation for a mixture containing 44 wt% HFC-125, 52 wt% HFC-143a (1 ,1 ,1 -trifluoroethane), and 4 wt% HFC-134a) has a GWP of 3922 and will be in need of replacement.
  • R-507A (ASHRAE designation for a mixture containing 50 wt% HFC-125 and 50 wt% HFC- 143a), which has virtually identical properties to R404A and can therefore be used in many R404A systems, has a GWP equal to 3985, and therefore does not provide a lower GWP replacement for R404A, but will be in need of replacement as well.
  • R407A (ASHRAE designation for a blend of 20 weight percent R32, 40 weight percent R125
  • compositions of the present invention provide low GWP replacements for all of these refrigerants currently in use.
  • the disclosed compositions may comprise optional non-refrigerant components.
  • the optional non-refrigerant components (also referred to herein as additives) in the compositions disclosed herein may comprise one or more components selected from the group consisting of lubricants, dyes (including UV dyes), solubilizing agents, compatibilizers, stabilizers, tracers, peril uoropolyethers, anti-wear agents, extreme pressure agents, corrosion and oxidation inhibitors, metal surface energy reducers, metal surface deactivators, free radical scavengers, foam control agents, viscosity index improvers, pour point depressants, detergents, viscosity adjusters, and mixtures thereof.
  • lubricants include silicone oils, silicone oils, and mixtures thereof.
  • one or more non-refrigerant components are present in small amounts relative to the overall composition.
  • the amount of additive(s) concentration in the disclosed compositions is from less than about 0.1 weight percent to as much as about 5 weight percent of the total composition. In some embodiments of the present invention, the additives are present in the disclosed
  • compositions in an amount between about 0.1 weight percent to about 5 weight percent of the total composition or in an amount between about 0.1 weight percent to about 3.5 weight percent.
  • component(s) selected for the disclosed composition is selected on the basis of the utility and/or individual equipment components or the system requirements.
  • the lubricant is a mineral oil lubricant.
  • the mineral oil lubricant is selected from the group consisting of paraffins (including straight carbon chain saturated hydrocarbons, branched carbon chain saturated hydrocarbons, and mixtures thereof), naphthenes (including saturated cyclic and ring structures), aromatics (those with unsaturated hydrocarbons containing one or more ring, wherein one or more ring is characterized by alternating carbon-carbon double bonds) and non-hydrocarbons (those molecules containing atoms such as sulfur, nitrogen, oxygen and mixtures thereof), and mixtures and combinations of thereof.
  • the synthetic lubricant is selected from the group consisting of alkyl substituted aromatics (such as benzene or naphthalene substituted with linear, branched, or mixtures of linear and branched alkyl groups, often generically referred to as alkylbenzenes), synthetic paraffins and naphthenes, poly (alpha olefins), polyglycols (including polyalkylene glycols), dibasic acid esters, polyesters, polyol esters, neopentyl esters, polyvinyl ethers (PVEs), silicones, silicate esters, fluorinated compounds, phosphate esters, polycarbonates and mixtures thereof, meaning mixtures of the any of the lubricants disclosed in this paragraph.
  • alkyl substituted aromatics such as benzene or naphthalene substituted with linear, branched, or mixtures of linear and branched alkyl groups, often generically referred to as alkylbenzenes
  • the lubricants as disclosed herein may be commercially available lubricants.
  • the lubricant may be paraffinic mineral oil, sold by BVA Oils as BVM 100 N, naphthenic mineral oils sold by Crompton Co. under the trademarks Suniso ® 1 GS, Suniso ® 3GS and Suniso ® 5GS, naphthenic mineral oil sold by Pennzoil under the trademark Sontex ® 372LT, naphthenic mineral oil sold by Calumet Lubricants under the trademark Calumet ® RO-30, linear alkylbenzenes sold by Shrieve
  • the lubricants used with the present invention may be designed for use with hydrofluorocarbon refrigerants and may be miscible with compositions as disclosed herein under compression refrigeration and air- conditioning apparatus' operating conditions.
  • the lubricants are selected by considering a given compressor's requirements and the environment to which the lubricant will be exposed.
  • the lubricant is present in an amount of less than 5.0 weight percent to the total composition. In other embodiments, the amount of lubricant is between about 0.1 and 3.5 weight percent of the total composition.
  • compositions disclosed herein may acquire additional lubricant from one or more equipment components of such heat transfer system.
  • lubricants may be charged in the compressor and/or the compressor lubricant sump.
  • Such lubricant would be in addition to any lubricant additive present in the refrigerant in such a system.
  • the refrigerant composition when in the compressor may pick up an amount of the equipment lubricant to change the refrigerant-lubricant composition from the starting ratio.
  • the entire system may contain a total composition with as much as about 75 weight percent to as little as about 1 .0 weight percent of the composition being lubricant.
  • the system may contain about 3 weight percent lubricant (over and above any lubricant present in the refrigerant composition prior to charging the system) and 97 weight percent refrigerant.
  • the non-refrigerant component used with the compositions of the present invention may include at least one dye.
  • the dye may be at least one ultra-violet (UV) dye.
  • the UV dye may be a fluorescent dye.
  • the fluorescent dye may be selected from the group consisting of
  • naphthalimides perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and
  • the disclosed compositions contain from about 0.001 weight percent to about 1 .0 weight percent UV dye. In other embodiments, the UV dye is present in an amount of from about
  • the UV dye is present in an amount of from 0.01 weight percent to about 0.25 weight percent of the total composition.
  • UV dye is a useful component for detecting leaks of the composition by permitting one to observe the fluorescence of the dye at or in the vicinity of a leak point in an apparatus (e.g., refrigeration unit, air-conditioner or heat pump).
  • the UV emission e.g., fluorescence from the dye may be observed under an ultra-violet light. Therefore, if a composition containing such a UV dye is leaking from a given point in an apparatus, the
  • fluorescence can be detected at the leak point, or in the vicinity of the leak point.
  • Another non-refrigerant component which may be used with the compositions of the present invention may include at least one solubilizing agent selected to improve the solubility of one or more dye in the disclosed compositions.
  • the weight ratio of dye to solubilizing agent ranges from about 99:1 to about 1 :1 .
  • the solubilizing agents include at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (such as dipropylene glycol dimethyl ether), amides, nitriles, ketones,
  • chlorocarbons such as methylene chloride, trichloroethylene, chloroform, or mixtures thereof
  • esters such as methylene chloride, trichloroethylene, chloroform, or mixtures thereof
  • lactones such as methylene chloride, trichloroethylene, chloroform, or mixtures thereof
  • the non-refrigerant component comprises at least one compatibilizer to improve the compatibility of one or more lubricants with the disclosed compositions.
  • the compatibilizer may be selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers (such as dipropylene glycol dimethyl ether), amides, nitriles, ketones, chlorocarbons (such as methylene chloride, trichloroethylene, chloroform, or mixtures thereof), esters, lactones, aromatic ethers, fluoroethers, 1 ,1 ,1 -trifluoroalkanes, and mixtures thereof, meaning mixtures of any of the compatibilizers disclosed in this paragraph.
  • the solubilizing agent and/or compatibilizer may be selected from the group consisting of hydrocarbon ethers consisting of the ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME) and mixtures thereof, meaning mixtures of any of the hydrocarbon ethers disclosed in this paragraph.
  • the compatibilizer may be linear or cyclic aliphatic or aromatic hydrocarbon compatibilizer containing from 6 to 15 carbon atoms.
  • the compatibilizer may be at least one hydrocarbon, which may be selected from the group consisting of at least hexanes, octanes, nonane, and decanes, among others. Commercially available hydrocarbon
  • compatibilizers include but are not limited to those from Exxon Chemical (USA) sold under the trademarks Isopar ® H, a mixture of undecane (Cn) and dodecane (C12) (a high purity Cn to C12 iso-paraffinic), Aromatic 150 (a Cg to O aromatic) (, Aromatic 200 (a Cg to C15 aromatic) and Naptha 140 (a mixture of C 5 to Cn paraffins, naphthenes and aromatic
  • the compatibilizer may alternatively be at least one polymeric compatibilizer.
  • the compatibilizer component contains from about 0.01 to 30 weight percent (based on total amount of compatibilizer) of an additive which reduces the surface energy of metallic copper, aluminum, steel, or other metals and metal alloys thereof found in heat exchangers in a way that reduces the adhesion of lubricants to the metal.
  • metal surface energy reducing additives include those commercially available from DuPont under the trademarks Zonyl ® FSA, Zonyl ® FSP, and Zonyl ® FSJ.
  • Another non-refrigerant component which may be used with the compositions of the present invention may be a metal surface deactivator.
  • the metal surface deactivator is selected from the group consisting of areoxalyl bis (benzylidene) hydrazide (CAS reg no. 6629-10-3), ⁇ , ⁇ '- bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoylhydrazine (CAS reg no. 32687-78-8) , 2,2,' - oxamidobis-ethyl-(3,5-di-tert-butyl-4- hydroxyhydrocinnamate (CAS reg no.
  • the non-refrigerant component used with the compositions of the present invention may alternatively be a stabilizer selected from the group consisting of hindered phenols, thiophosphates, butylated
  • tnphenylphosphorothionates organo phosphates, or phosphites
  • aryl alkyl ethers terpenes, terpenoids
  • epoxides fluorinated epoxides
  • oxetanes ascorbic acid
  • thiols lactones
  • thioethers amines
  • nitromethane alkylsilanes
  • benzophenone derivatives aryl sulfides, divinyl terephthalic acid, diphenyl terephthalic acid, ionic liquids, and mixtures thereof, meaning mixtures of any of the stabilizers disclosed in this paragraph.
  • the stabilizer may be selected from the group consisting of tocopherol; hydroquinone; t-butyl hydroquinone; monothiophosphates; and
  • dithiophosphates commercially available from Ciba Specialty Chemicals, Basel, Switzerland, hereinafter "Ciba", under the trademark Irgalube ® 63; dialkylthiophosphate esters, commercially available from Ciba under the trademarks Irgalube ® 353 and Irgalube ® 350, respectively; butylated tnphenylphosphorothionates, commercially available from Ciba under the trademark Irgalube ® 232; amine phosphates, commercially available from Ciba under the trademark Irgalube ® 349 (Ciba); hindered phosphites, commercially available from Ciba as Irgafos ® 168 and Tris-(di-tert- butylphenyl)phosphite, commercially available from Ciba under the trademark Irgafos ® OPH; (Di-n-octyl phosphite); and iso-de
  • isopropylated triphenyl phosphates such as those commercially available under the trademarks Durad ® 220 and Durad ® 1 10; anisole; 1 ,4- dimethoxybenzene; 1 ,4-diethoxybenzene; 1 ,3,5-trimethoxybenzene;
  • pinene pinene; menthol; geraniol; farnesol; phytol; Vitamin A; terpinene; delta-3- carene; terpinolene; phellandrene; fenchene; dipentene; caratenoids, such as lycopene, beta carotene, and xanthophylls, such as zeaxanthin;
  • retinoids such as hepaxanthin and isotretinoin; bornane; 1 ,2-propylene oxide; 1 ,2-butylene oxide; n-butyl glycidyl ether; trifluoromethyloxirane; 1 ,1 -bis(trifluoromethyl)oxirane; 3-ethyl-3-hydroxymethyl-oxetane, such as OXT-101 (Toagosei Co., Ltd); 3-ethyl-3-((phenoxy)methyl)-oxetane, such as OXT-21 1 (Toagosei Co., Ltd); 3-ethyl-3-((2-ethyl-hexyloxy)methyl)- oxetane, such as OXT-212 (Toagosei Co., Ltd); ascorbic acid;
  • methanethiol (methyl mercaptan); ethanethiol (ethyl mercaptan);
  • Coenzyme A dimercaptosuccinic acid (DMSA); grapefruit mercaptan ((R)- 2-(4-methylcyclohex-3-enyl)propane-2-thiol)); cysteine (( R)-2-amino-3- sulfanyl-propanoic acid); lipoamide (1 ,2-dithiolane-3-pentanamide); 5,7- bis(1 ,1 -dimethylethyl)-3-[2,3(or 3,4)-dimethylphenyl]-2(3H)-benzofuranone, commercially available from Ciba under the trademark Irganox ® HP-136; benzyl phenyl sulfide; diphenyl sulfide; diisopropylamine; dioctadecyl 3,3'- thiodipropionate, commercially available from Ciba under the trademark Irganox ® PS 802 (Ciba); didodec
  • vinylthmethoxysilane 2,5-difluorobenzophenone; 2',5'- dihydroxyacetophenone; 2-aminobenzophenone; 2-chlorobenzophenone; benzyl phenyl sulfide; diphenyl sulfide; dibenzyl sulfide; ionic liquids; and mixtures and combinations thereof.
  • the additive used with the compositions of the present invention may alternatively be an ionic liquid stabilizer.
  • the ionic liquid stabilizer may be selected from the group consisting of organic salts that are liquid at room temperature (approximately 25 °C), those salts containing cations selected from the group consisting of pyridinium, pyridazinium, pyrimidinium, pyrazinium, imidazolium, pyrazolium, thiazolium, oxazolium and triazolium and mixtures thereof ; and anions selected from the group consisting of [BF ]-, [PF 6 ]-, [SbF 6 ]-, [CF 3 SO 3 ]-, [HCF 2 CF 2 SO 3 ]-, [CF 3 HFCCF 2 SO 3 ]-, [HCCIFCF 2 SO 3 ]-, [(CF 3 SO 2 ) 2 N]-, [(CF 3 CF 2 SO 2 ) 2 N]-, [(CF 3 SO 2 ) 3
  • ionic liquid stabilizers are selected from the group consisting of emim BF 4 (1 - ethyl-3-methylimidazolium tetrafluoroborate); bmim BF (1 -butyl-3- methylimidazolium tetraborate); emim PF 6 (1 -ethyl-3-methylimidazolium hexafluorophosphate); and bmim PF 6 (1 -butyl-3-methylimidazolium hexafluorophosphate), all of which are available from Fluka (Sigma- Aldrich).
  • the stabilizer may be a hindered phenol, which is any substituted phenol compound, including phenols comprising one or more substituted or cyclic, straight chain, or branched aliphatic substituent group, such as, alkylated monophenols including 2,6-di-tert-butyl-4- methylphenol; 2,6-di-tert-butyl-4-ethylphenol; 2,4-dimethyl-6- tertbutylphenol; tocopherol; and the like, hydroquinone and alkylated hydroquinones including t-butyl hydroquinone, other derivatives of hydroquinone; and the like, hydroxylated thiodiphenyl ethers, including 4,4'-thio-bis(2-methyl-6-tert-butylphenol); 4,4'-thiobis(3-methyl-6- tertbutylphenol); 2,2'-thiobis(4methyl-6-tert-butylphenol); and the like, alkyliden
  • the non-refrigerant component which is used with compositions of the present invention may alternatively be a tracer.
  • the tracer may be two or more tracer compounds from the same class of compounds or from different classes of compounds.
  • the tracer is present in the compositions at a total concentration of about 50 parts per million by weight (ppm) to about 1000 ppm, based on the weight of the total composition.
  • the tracer is present at a total concentration of about 50 ppm to about 500 ppm.
  • the tracer is present at a total concentration of about 100 ppm to about 300 ppm.
  • the tracer may be selected from the group consisting of
  • HFCs hydrofluorocarbons
  • deuterated hydrofluorocarbons deuterated hydrofluorocarbons
  • the tracer may be selected from the group consisting of fluoroethane, 1 ,1 ,-difluoroethane, 1 ,1 ,1 - trifluoroethane, 1 ,1 ,1 ,3,3,3-hexafluoropropane, 1 ,1 ,1 ,2,3,3,3- heptafluoropropane, 1 ,1 ,1 ,3,3-pentafluoropropane, 1 ,1 ,1 ,3,3- pentafluorobutane, 1 ,1 ,1 ,2,3,4,4,5,5,5-decafluoropentane,
  • the tracer is a blend containing two or more hydrofluorocarbons, or one hydrofluorocarbon in combination with one or more perfluorocarbons.
  • the tracer may be added to the compositions of the present invention in predetermined quantities to allow detection of any dilution
  • the additive which may be used with the compositions of the present invention may alternatively be a peril uoropolyether as described in detail in US2007-0284555, incorporated herein by reference.
  • the refrigerant mixtures and the compositions of this invention containing them contain no more than about 0.5 weight percent of the refrigerants other than HFO-1234yf, HFC-32, trans-HFO-1234ze and when present HFC-152.
  • compositions disclosed herein may be prepared by any convenient method to combine the desired amounts of the individual components.
  • a preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.
  • compositions of the present invention have zero ozone depletion potential and low global warming potential (GWP). Additionally, the compositions of the present invention will have global warming potentials that are less than many hydrofluorocarbon refrigerants currently in use.
  • One aspect of the present invention is to provide a refrigerant with a global warming potential of less than 1000, less than 600, less than 500, less than 400, less than 300, less than 150, less than 100, or less than 50.
  • compositions disclosed herein are useful as heat transfer compositions or refrigerants.
  • the compositions comprising HFO-1234yf, HFC-32 and HFO-1234ze and optionally HFC-152a are useful as refrigerants.
  • the compositions comprising HFO-1234yf, HFC-32 and HFO-1234ze and optionally HFC-152a are useful as replacements for R404A, R407A, R407F or R507A in refrigeration systems.
  • Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device.
  • a refrigeration cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step.
  • the cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator, by withdrawing heat from the environment, at a low temperature to form a gas and produce cooling. Often air or a heat transfer fluid flows over or around the evaporator to transfer the cooling effect caused by the evaporation of the refrigerant in the evaporator to a body to be cooled.
  • the low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature.
  • the higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment.
  • the refrigerant returns to the expansion device through which the liquid expands from the higher- pressure level in the condenser to the low-pressure level in the
  • the method comprises replacing said R404A, R407A, R407F or R507A with a refrigerant of the present invention consisting of HFO-1234yf, HFC-32 and trans-HFO-1234ze, and optionally HFC-152a.
  • refrigeration equipment suitable for using R404A, R407A, R407F or R507A as a refrigerant is provided.
  • the method comprises producing refrigeration in said equipment using a refrigerant of the present invention consisting of HFO-1234yf, HFC-32 and trans-HFO-1234ze and optionally HFC-152a as refrigerant.
  • a refrigeration apparatus containing a refrigerant composition and suitable for using a refrigerant composition wherein R404A, R407A, R407F or R507A is the refrigerant component of said refrigerant composition.
  • the apparatus is characterized by: containing the refrigerant composition of the present invention consisting of HFO-1234yf, HFC-32 and trans-HFO-1234ze, and optionally HFC-152a.
  • a refrigerant apparatus containing a refrigerant composition and including an evaporator designed for a refrigerant evaporation temperature between about -40°C and about 0°C is provided.
  • the apparatus is characterized by: containing the refrigerant composition of the present invention consisting of HFO-1234yf, HFC-32, and trans- HFO-1234ze, and optionally HFC-152a.
  • a process for producing cooling comprising condensing a refrigerant mixture as disclosed herein and thereafter evaporating said composition in the vicinity of a body to be cooled.
  • a body to be cooled may be defined as any space, location, object or body for which it is desirable to provide cooling. Examples include spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket.
  • vicinity By vicinity is meant that the evaporator of the system containing the refrigerant mixture is located either within or adjacent to the body to be cooled, such that air moving over the evaporator would move into or around the body to be cooled.
  • the refrigerant mixtures as disclosed herein may be useful in particular in refrigeration applications including medium or low temperature refrigeration.
  • Medium temperature refrigeration systems includes supermarket and convenience store refrigerated cases for beverages, dairy, fresh food transport and other items requiring refrigeration.
  • Low temperature refrigeration systems include supermarket and convenience store freezer cabinets and displays, ice machines and frozen food transport. Other specific uses may be in commercial, industrial or residential refrigerators and freezers, ice machines, self- contained coolers and freezers, supermarket rack and distributed systems, walk-in and reach-in coolers and freezers, and combination systems. Of particular note are low temperature refrigeration systems containing the compositions of the present invention.
  • the disclosed compositions may function as primary refrigerants in secondary loop systems that provide cooling to remote locations by use of a secondary heat transfer fluid, which may comprise water, a glycol, carbon dioxide, or a fluorinated hydrocarbon fluid.
  • a secondary heat transfer fluid which may comprise water, a glycol, carbon dioxide, or a fluorinated hydrocarbon fluid.
  • the secondary heat transfer fluid is the body to be cooled as it is adjacent to the evaporator and is cooled before moving to a remote body to be cooled.
  • compositions disclosed herein may be useful as low GWP (global warming potential) replacements for currently used refrigerants, including R404A (ASHRAE designation for a blend of 44 weight percent R125, 52 weight percent R143a (1 ,1 ,1 -trifluoroethane), and 4.0 weight percent R134a); R407A (ASHRAE designation for a blend of 20 weight percent R32, 40 weight percent R125 (pentafluoroethane), and 40 weight percent R134a); R407F (ASHRAE designation for a blend of 30 weight percent R32, 30 weight percent R125 (pentafluoroethane), and 40 weight percent R134a) and R-507A (ASHRAE designation for a blend of 50 weight percent R125 and 50 weight percent R143a).
  • R404A ASHRAE designation for a blend of 44 weight percent R125, 52 weight percent R143a (1 ,1 ,1 -trifluoroethane), and 4.0 weight percent R134a
  • R407A
  • compositions as disclosed herein may be useful as replacements for R404A, R407A, R407F or R507A in equipment designed for R404A, R407A, R407F or R507A with some system modifications.
  • compositions as disclosed herein comprising HFO-1234yf, HFC-32, and trans-HFO-1234ze, and optionally HFC-152a may be useful for replacing R404A, R407A, R407F or R507A in equipment specifically modified for or produced entirely for these new compositions comprising HFO-1234yf, HFC-32, and trans-HFO-1234ze, and optionally HFC-152a.
  • compositions are useful as refrigerants and provide at least comparable cooling performance (meaning cooling capacity and energy efficiency) as the refrigerant for which a replacement is being sought.
  • a method for replacing a refrigerant selected from the group consisting of R404A, R407A, R407F and R507A comprises charging a refrigeration apparatus with a refrigerant mixture comprising HFO-1234yf, HFC-32, and trans-HFO- 1234ze, and optionally HFC-152a as described herein.
  • the refrigeration apparatus is suitable for use with in of R404A, R407A, R407F or R507A.
  • the refrigeration apparatus is suitable for use with in of R404A, R407A, R407F or R507A.
  • the refrigeration apparatus is suitable for use with in of R404A, R407A, R407F or R507A.
  • refrigeration apparatus includes systems with evaporating temperatures in the range of from about -40°C to about 0°C. Of note are embodiments wherein the refrigeration apparatus includes systems with evaporating temperatures in the range of from about -40°C to about -20°C. Also of note are embodiments wherein the refrigeration apparatus includes systems with evaporating temperatures in the range of from about -20°C to about 0°C
  • a method for recharging a heat transfer system that contains a refrigerant to be replaced and a lubricant comprising removing the refrigerant to be replaced from the heat transfer system while retaining a substantial portion of the lubricant in said system and introducing one of the compositions herein disclosed to the heat transfer system.
  • a heat exchange system comprising a composition disclosed herein, wherein said system is selected from the group consisting of freezers, refrigerators, walk-in coolers, super market refrigeration or freezer systems, mobile refrigerators, and systems having combinations thereof.
  • a heat transfer system containing a composition as disclosed herein.
  • a refrigeration apparatus containing a composition as disclosed herein.
  • a stationary refrigeration apparatus containing a composition as disclosed herein.
  • a medium temperature refrigeration apparatus containing the composition of the present invention.
  • a low temperature refrigeration apparatus containing the composition of the present invention.
  • the apparatus typically includes an evaporator, a compressor, a condenser, and an expansion device.
  • a mobile refrigeration apparatus containing a composition as disclosed herein.
  • Compositions of the present invention are evaluated under vapor leak conditions as described under ASHRAE Standard 34 "Designation and Safety Classification of Refrigerants" to evaluate scenarios whereby requirements could be met for an Occupational Exposure Limit (OEL) of at least 400 ppm. This would allow an ASHRAE Class A lower toxicity rating which is preferred by the HVAC&R industry. Per the standard, nominal formulations are developed and then assigned manufacturing tolerances (as exact formulations are not made in commercial practice). The Worst Case Formulation (WCF) is selected to represent the formulation that could be most toxic based on the OELs of the individual components.
  • WCF Worst Case Formulation
  • the change to the WCF is determined for vapor leak at worst case conditions, which in the case of the compositions of the present invention is the bubble point of the WCF + 10 degrees C per the standard or -40 degrees C whichever is higher. Vapor leak conditions are continued until the formulation reaches atmospheric pressure (for this example after about 53-63% leakage), and the Worst Case Fractionated Formulation (WCFF) is determined indicating the residual liquid or vapor composition which is expected to be the most flammable or most toxic. If the OEL is above 400 ppm and the WCFF is expected to be non-flammable, it is considered a preferred mixture.
  • Results are shown in Table 1 below for a range of potential OELs for HFO-1234yf at 50 ppm, 100 ppm, 150 ppm and 200 ppm and compositions are adjusted accordingly to meet Class A requirements.
  • GWP has also been calculated based on IPCC AR4 values where available.
  • compositions of the present invention containing HFO-1234yf, HFC-32 and trans-HFO-1234ze provide nominal
  • compositions as well as, WCFF compositions with OEL which exceed 400 ppm indicating Class A lower toxicity per ASHRAE Standard 34.
  • compositions have burning velocities less than 10 cm/sec establishing 2L lower flammability classification according to ASHRAE Standard 34, because the burning velocity of all components is less than 10 cm/sec
  • Cooling performance for compositions of the present invention is determined and displayed in Table 2 as compared to R-404A; R-507A; R- 407F; and R-407A.
  • Compressor discharge temperatures, COP (energy efficiency) and cooling capacity (cap) are calculated from physical property measurements for the following specific conditions:
  • compositions of the present invention would serve as good replacements for R-404A, R-507A, R-407A and R-407F. These compositions show cooling capacity within about 10% of current refrigerants and improved energy efficiency versus R-404A, R- 507A and R-407A. They also have significantly reduced GWP. Therefore, compositions of the present invention provide the best balance of properties as replacements for R-404A, R-507A, R-407F and R-407A.
  • compositions of the present invention are evaluated under vapor leak conditions as described above in Examples 1 . Vapor leak conditions are continued until the formulation reaches atmospheric pressure (for this example, after about 55-65% leakage), and the Worst Case Fractionated Formulation (WCFF) is determined indicating the residual liquid or vapor composition which is expected to be the most toxic.
  • the OEL for the WCFF is calculated. If it is above 400 ppm, the composition may be classified as a Class A toxicity (lower toxicity). Results are shown in Table 5 below for OELs for HFO-1234yf at 50 ppm and 100 ppm. Additionally, estimated burning velocities are provided in Table 5 (see procedure for estimating burning velocities at the end of the examples).
  • compositions of the present invention containing HFO-1234yf, HFC-32, HFC-152a and trans-HFO-1234ze provide nominal compositions, as well as, WCFF compositions with OEL which exceed 400 ppm indicating Class A lower toxicity per ASHRAE Standard 34.
  • compositions have estimated burning velocities less than 10 cm/sec indicating 2L lower flammability classification according to ASHRAE Standard 34.
  • Cooling performance for compositions of the present invention is determined and displayed in Table 4 as compared to R-404A; R-507A; R- 407F; and R-407A.
  • Compressor discharge temperatures, COP (energy efficiency) and cooling capacity (cap) are calculated from physical property measurements for the following specific conditions:
  • compositions of the present invention would serve as good replacements for R-404A, R-507A, R-407A and R-407F. These compositions show cooling capacity within about 10% of current refrigerants and improved energy efficiency versus R-404A, R-507A and R-407A. They also have reduced GWP. Therefore, compositions of the present invention provide the best balance of properties as replacements for R-404A, R-507A, R-407F and R-407A.
  • compositions containing HFO-1234yf, HFC-32, and trans-HFO- 1234ze are evaluated under vapor leak conditions as described above in Examples 1 . Vapor leak conditions are continued until the formulation reaches atmospheric pressure (for this example, after about 67-97% leakage), and the Worst Case Fractionated Formulation (WCFF) is determined indicating the residual liquid or vapor composition which is expected to be the most toxic.
  • the OEL for the WCFF is calculated. If it is above 400 ppm, the composition may be classified as a Class A toxicity (lower toxicity). Results are shown in Table 5 below for OELs for HFO- 1234yf at 50 ppm and 100 ppm.
  • compositions A through G produce WCFF compositions during leakage that have OEL less than 400. Thus these compositions would be classified by ASHRAE as Class B, higher toxicity refrigerants.
  • compositions containing HFO-1234yf, HFC-32, trans-HFO- 1234ze and HFC-152a are evaluated under vapor leak conditions as described above in Example 1 . Vapor leak conditions are continued until the formulation reaches atmospheric pressure (after about 67-97% leakage), and the Worst Case Fractionated Formulation (WCFF) is determined indicating the residual liquid or vapor composition which is expected to be the most toxic.
  • the OEL for the WCFF is calculated. If it is above 400 ppm, the composition may be classified as a Class A toxicity (lower toxicity). Results are shown in Table 5 below for OELs for HFO- 1234yf at 50 ppm and 100 ppm. Additionally, estimated burning velocities (BV) are shown in Table 5 for the initial composition and for the WCFF composition for each case (see procedure for estimating burning velocities at the end of the examples).
  • compositions containing HFO1234yf, HFC- 152a, and HFC-32 were estimated using an equation generated by measuring the pressure rise in a 12-liter vessel relative to the pressure rise produced by R-32 during an ignition.
  • Compositions were introduced at stoichiometric amounts in air into the 12-liter vessel at 25°C and atmospheric pressure.
  • the compositions were ignited using a fused-Ni- chrome wire-igniter and the time to reach a pressure of 2 atmospheres was measured.
  • the ratio of the time for each composition relative to the time for R-32 to reach 2 atm was reported. This value was then used to estimate a burning velocity for each mixture assuming that R-32 burning velocity is 6.7 cm/s. Results are shown in Table 7 below:
  • FIG. 2 represents a plot of the estimated burning velocities (as listed in Table 7 and 7.1 ) versus the ratio of wt% HFO-1234 (meaning HFO- 1234yf, trans-HFO-1234ze or a combination thereof) to wt% HFC-152a for compositions containing HFO-1234, HFC-32 and HFC-152a.
  • the equation from FIG. 2 was then used to estimate burning velocity for compositions based on the ratio, wt% HFO-1234/wt% HFC-152a. These values for burning velocity are those provided in the examples herein.
  • Embodiment A1 A composition consisting of (A) a refrigerant component consisting essentially of (1 ) at least one refrigerant having an OEL less than 400; and (2) a combination of refrigerants, each having an OEL greater than 400, consisting essentially of (i) at least one refrigerant selected from the group consisting of HFC-32 and HFC-152a; and (ii) trans-HFO-1234ze; and optionally (B) a non-refrigerant component;
  • component (A)(2) of the refrigerant component is present in an amount sufficient to provide an overall OEL for the refrigerant component of at least 400.
  • Embodiment A2 The composition according to Embodiment A1 wherein the worst case fractionation formulation of the refrigerant component has an overall OEL of at least 400.
  • Embodiment A3 The composition of any of Embodiments A1 -A2 wherein the refrigerant component has a GWP of less than 600.
  • Embodiment A4 The composition of any of embodiments A1 -A3 wherein the refrigerant component has a GWP of less than 500.
  • Embodiment A5. The composition of any of embodiments A1 -A4 wherein the refrigerant component has a GWP of less than 300.
  • Embodiment A6 The composition of any of embodiments A1 -A5 wherein component (A)(1 ) is selected from olefinic refrigerants.
  • Embodiment A7 The composition of any of embodiments A1 -A5 wherein component (A)(1 ) consists essentially of HFO-1234yf.
  • Embodiment A8 The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R404A, R407A, R407F or R507A and consists essentially of from 4 to 16 weight percent of HFO-1234yf, from 34 to 38 weight percent of 32, and from 48 to 60 weight percent of trans-HFO-1234ze.
  • Embodiment A8a The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R404A and consists essentially of from 4 to 16 weight percent of HFO- 1234yf, from 34 to 38 weight percent of 32, and from 48 to 60 weight percent of trans-HFO-1234ze.
  • Embodiment A8b The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R407A and consists essentially of from 4 to 16 weight percent of HFO- 1234yf, from 34 to 38 weight percent of 32, and from 48 to 60 weight percent of trans-HFO-1234ze.
  • Embodiment A8c The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R407F and consists essentially of from 4 to 16 weight percent of HFO-1234yf, from 34 to 38 weight percent of 32, and from 48 to 60 weight percent of trans-HFO-1234ze.
  • Embodiment A8d The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R507A and consists essentially of from 4 to 16 weight percent of HFO- 1234yf, from 34 to 38 weight percent of 32, and from 48 to 60 weight percent of trans-HFO-1234ze.
  • Embodiment A9. The composition of any of embodiments A1 -A8 wherein the burning velocity of the overall refrigerant component is less than 10 cm/sec.
  • Embodiment A10 The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R404A, R407A, R407F or R507A and consists essentially of from 5 to 9 weight percent of HFO-1234yf, from 34 to 38 weight percent of 32, from 1 to 16 weight percent of HFC-152a, and from 41 to 45 weight percent of trans-HFO-1234ze; wherein the burning velocity of the overall refrigerant component is less than 10 cm/sec.
  • Embodiment A10a The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R404A and consists essentially of from 5 to 9 weight percent of HFO- 1234yf, from 34 to 38 weight percent of 32, from 1 to 16 weight percent of HFC-152a, and from 41 to 45 weight percent of trans-HFO-1234ze;
  • burning velocity of the overall refrigerant component is less than 10 cm/sec.
  • Embodiment A10b The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R407A and consists essentially of from 5 to 9 weight percent of HFO-
  • Embodiment A10c The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R407F and consists essentially of from 5 to 9 weight percent of HFO- 1234yf, from 34 to 38 weight percent of 32, from 1 to 16 weight percent of HFC-152a, and from 41 to 45 weight percent of trans-HFO-1234ze;
  • Embodiment A10d The composition of any of embodiments A1 -A7 wherein the refrigerant component is suitable for use as a replacement for R507A and consists essentially of from 5 to 9 weight percent of HFO- 1234yf, from 34 to 38 weight percent of 32, from 1 to 16 weight percent of HFC-152a, and from 41 to 45 weight percent of trans-HFO-1234ze;
  • burning velocity of the overall refrigerant component is less than 10 cm/sec.
  • Embodiment A1 1 The composition of any of embodiments A1 -A10 wherein component (A)(1 ) is selected from refrigerants which have an OEL of about 100 or less.
  • Embodiment A12 The composition of any of embodiments A1 -A1 1 wherein component (A)(1 ) is selected from refrigerants which have an OEL of about 50 or less.
  • Embodiment A13 The composition of any of embodiments A1 -A12 wherein component (A)(1 ) is selected from refrigerants which have an OEL of about 100 or less.
  • Embodiment B1 A method for replacing R404A, R407A, R407F or R507A in refrigeration equipment including an evaporator designed for a refrigerant evaporation temperature between about -40°C and about 0°C, comprising replacing said R404A, R407A, R407F or R507A with a composition of any of embodiments A1 -A8 or A10.
  • Embodiment B2 A method for replacing R404A, R407A, R407F or R507A in refrigeration equipment including an evaporator designed for a refrigerant evaporation temperature between about -40°C and about 0°C, comprising replacing said R404A with a composition of any of
  • Embodiment B3 A method for replacing R404A, R407A, R407F or R507A in refrigeration equipment including an evaporator designed for a refrigerant evaporation temperature between about -40°C and about 0°C, comprising replacing said R407A with a composition of any of
  • Embodiment B4 A method for replacing R404A, R407A, R407F or R507A in refrigeration equipment including an evaporator designed for a refrigerant evaporation temperature between about -40°C and about 0°C, comprising replacing said R407F with a composition of any of
  • Embodiment B5. A method for replacing R404A, R407A, R407F or R507A in refrigeration equipment including an evaporator designed for a refrigerant evaporation temperature between about -40°C and about 0°C, comprising replacing said R507A with a composition of any of
  • Embodiment C1 A method for producing refrigeration in refrigeration equipment suitable for using R404A, R407A, R407F or R507A as a refrigerant comprising producing refrigeration in said equipment using a composition of any of embodiments A1 -A8 or A10 as a refrigerant.
  • Embodiment C2. A method for producing refrigeration in refrigeration equipment suitable for using R404A as a refrigerant comprising producing refrigeration in said equipment using a composition of any of embodiments A1 -A8 or A10 as a refrigerant.
  • Embodiment C3 A method for producing refrigeration in refrigeration equipment suitable for using R407A as a refrigerant comprising producing refrigeration in said equipment using a composition of any of embodiments A1 -A8 or A10 as a refrigerant.
  • Embodiment C4 A method for producing refrigeration in refrigeration equipment suitable for using R407F as a refrigerant comprising producing refrigeration in said equipment using a composition of any of embodiments A1 -A8 or A10 as a refrigerant.
  • Embodiment C5. A method for producing refrigeration in refrigeration equipment suitable for using R507A as a refrigerant comprising producing refrigeration in said equipment using a composition of any of embodiments A1 -A8 or A10 as a refrigerant.
  • Embodiment D1 . A refrigeration apparatus containing a refrigerant composition and suitable for using a refrigerant composition wherein R404A, R407A, R407F or R507A is the refrigerant component of said refrigerant composition, characterized by: containing the refrigerant composition of any of embodiments A1 -A8 or A10.
  • Embodiment D2 A refrigeration apparatus containing a refrigerant composition and suitable for using a refrigerant composition wherein R404A is the refrigerant component of said refrigerant composition, characterized by: containing the refrigerant composition of any of embodiments A1 -A8 or A10.
  • Embodiment D3 A refrigeration apparatus containing a refrigerant composition and suitable for using a refrigerant composition wherein R407A is the refrigerant component of said refrigerant composition, characterized by: containing the refrigerant composition of any of embodiments A1 -A8 or A10.
  • Embodiment D4 A refrigeration apparatus containing a refrigerant composition and suitable for using a refrigerant composition wherein R407F is the refrigerant component of said refrigerant composition, characterized by: containing the refrigerant composition of any of embodiments A1 -A8 or A10.
  • Embodiment D5 A refrigeration apparatus containing a refrigerant composition and suitable for using a refrigerant composition wherein R507A is the refrigerant component of said refrigerant composition, characterized by: containing the refrigerant composition of any of embodiments A1 -A8 or A10.
  • Embodiment E1 A refrigerant apparatus containing a refrigerant composition and including an evaporator designed for a refrigerant evaporation temperature between about -40°C and about 0°C characterized by: containing the refrigerant composition of any of embodiments A1 -A8 or A10.
  • Embodiment F1 A process for producing cooling comprising condensing a refrigerant component of a composition of any of embodiments A1 -A8 or A10 and thereafter evaporating said refrigerant component in the vicinity of a body to be cooled.
  • Embodiment G1 Use of a composition of any of embodiments A1 -A8 or A10 as a refrigerant in equipment suitable for use with R404A, R407A, R407F or R507A.
  • Embodiment G2 Use of a composition of any of embodiments A1 -A8 or A10 as a refrigerant in equipment suitable for use with R404A.
  • Embodiment G3. Use of a composition of any of embodiments A1 -A8 or A10 as a refrigerant in equipment suitable for use with R407A.
  • Embodiment G1 Use of a composition of any of embodiments A1 -A8 or A10 as a refrigerant in equipment suitable for use with R407F.
  • Embodiment G1 Use of a composition of any of embodiments A1 -A8 or A10 as a refrigerant in equipment suitable for use with R507A.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)

Abstract

Cette invention concerne des compositions, lesdites compositions comprenant : (A) un constituant réfrigérant constitué essentiellement de (1) au moins un réfrigérant ayant un OEL inférieur à 400; et (2) une combinaison de réfrigérants, ayant chacun un OEL supérieur à 400, essentiellement constituée de (i) au moins un réfrigérant choisi dans le groupe comprenant HFC-32 et HFC-152a; et (ii) un trans-HFO-1234ze; et éventuellement (B) un constituant de type non-réfrigérant, le constituant (A)(2) du constituant réfrigérant étant présent en une quantité suffisante pour obtenir un OEL global pour le constituant réfrigérant d'au moins 400. Les mélanges de réfrigérants du réfrigérant sont utiles à titre de constituants dans des compositions contenant également des non-réfrigérants (par ex. lubrifiants), dans des procédés destinés à produire de la réfrigération, dans des procédés de remplacement du réfrigérant R404A, R407A, R407F ou R-507A, et dans un appareil de réfrigération.
PCT/US2013/056396 2012-08-23 2013-08-23 Mélanges de réfrigérants comprenant des tétrafluoropropènes, du difluorométhane, et éventuellement du difluoroéthane et leurs utilisations WO2014031962A1 (fr)

Priority Applications (3)

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EP13831214.5A EP2888334B1 (fr) 2012-08-23 2013-08-23 Mélanges de réfrigérants comprenant des tétrafluoropropènes et du difluorométhane et leurs utilisations
ES13831214T ES2703937T3 (es) 2012-08-23 2013-08-23 Mezclas refrigerantes que comprenden tetrafluoropropenos y difluorometano y sus usos
PL13831214T PL2888334T3 (pl) 2012-08-23 2013-08-23 Mieszaniny czynnika chłodniczego zawierające tetrafluoropropeny i difluorometan i ich zastosowania

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US201261692314P 2012-08-23 2012-08-23
US61/692,314 2012-08-23

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EP4070750A1 (fr) 2013-10-15 2022-10-12 Autonomix Medical, Inc. Systèmes et méthodes de traitement du cancer et/ou d'augmentation de la fonction d'un organe
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EP4248897A2 (fr) 2014-12-04 2023-09-27 Autonomix Medical, Inc. Systèmes et méthodes de traitement du cancer et/ou d'augmentation de la fonction d'un organe

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EP2888334A4 (fr) 2015-09-16
ES2703937T3 (es) 2019-03-13
PL2888334T3 (pl) 2019-05-31
EP2888334A1 (fr) 2015-07-01
EP2888334B1 (fr) 2018-10-10
TW201412965A (zh) 2014-04-01

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